Insectidical nitro-substituted heterocyclic compounds

ABSTRACT

Nitro-substituted heterocyclic compounds of the formula (I) ##STR1## wherein R is hydrogen or alkyl, Z is an optionally substituted aryl or optionally substituted heterocyclic group containing at least one atom selected from N, O and S, 
     A is optionally substituted ethylene or optionally substituted trimethylene, and 
     B stands for 2 or 3 members of a heterocyclic ring which is formed, together with the adjacent C-atom and N-atom and at least one of said members may represent a hetero atom and may be optionally substituted, provided that when B stands for 3 members, two of which are carbon atoms and the other one is a nitrogen atom which is located in the middle of the three members, then at least one of said two carbon atoms must be substituted by a keto group. Such compounds being useful as insecticides.

This is a division of application Ser. No. 07/353,370 filed May 17, 1989now U.S. Pat. No. 4,960,780, which in turn was a division of applicationSer. No. 07/208,421, filed June 17, 1988, now U.S. Pat. No. 4,876,263,issued Oct. 24, 1984.

The present invention relates to novel nitro-substituted heterocycliccompounds, to processes for their preparation and to their use asinsecticides.

The following nitro-substituted heterocyclic compounds of the formulae(A) to (E) have already been disclosed in literature: ##STR2##

There have now been found novel nitro-substituted heterocyclic compoundsof the formula (I): ##STR3## wherein R is hydrogen or alkyl,

Z is an optionally substituted aryl or optionally substitutedheterocyclic group containing at least one atom selected from N, O andS,

A is optionally substituted ethylene or optionally substitutedtrimethylene radical, and

B stands for 2 or 3 members of a heterocyclic ring which is formed,together with the adjacent C-atom and N-atom and at least one of saidmembers may represent a hetero atom and may be optionally substituted,provided that when B stands for 3 members, two of which are carbon atomsand the other one is a nitrogen atom which is located in the middle ofthe three members, then at least one of said carbon atoms must besubstituted by a keto group.

The compounds of the formula (I) can be obtained by a process in which

a) compounds of the formula (II) ##STR4## wherein R and Z respectivelyhave the same meanings as above, M represents halogen, or --OSO₂ --L inwhich L denotes alkyl or aryl which may be substituted,

are reacted with compounds of the formula (III); ##STR5## wherein A andB are as defined above, in the presence of inert solvents and ifappropriate in the presence of a base, or

(b) [When B in the formula (I) is ##STR6## (the symbol "←" denotes alinkage between B and the adjacent nitrogen atom), then B is replacedwith B'.]

compounds of the formula (IV) ##STR7## wherein R, Z and A are the sameas above, are reacted with compounds represented by the followingformula (V) ##STR8## wherein R¹ is the same as above, glyoxalrepresented by the following formula (VI), ##STR9## glyoxylic acidrepresented by the following formula (VII), ##STR10## wherein R² is thesame as above, chlorothioformyl chloride represented by the followingformula (VIII), ##STR11## oxalyl chloride represented by the followingformula (IX), ##STR12## malonyl chloride represented by the followingformula (X), ##STR13## 4-chlorobenzene-sulfonylazide represented by thefollowing formula (XI), ##STR14## acrylic acid alkyl represented by thefollowing formula (XII),

    CH.sub.2 --CH--COOR.sup.2                                  (XII)

wherein R² is the same as above,

propiolic acid alkyl represented by the following formula (XIII),

    CH.tbd.CCOOR.sup.2                                         (XIII)

wherein R² is the same as above,

acetylene dicarboxylic acid dialkyl represented by the following formula(XIV),

    R.sup.2 OOCC.tbd.CCOOR.sup.2                               (XIV)

wherein R² is the same as above,

halopropionitrile represented by the following formula (XV),

    Hal--CH.sub.2 CH.sub.2 CN                                  (XV)

wherein Hal is a halogen atom,

or chlorocarbonyl isocyanate represented by the following formula (XVI),##STR15##

The nitro-substituted heterocyclic compounds of the formula (I)according to the present invention exhibit strong insecticidalactivities.

It is moreover surprising that the nitro-substituted heterocycliccompounds of the formula (I) according to the present invention exhibitconsiderably improved insecticidal activities as compared with the knowncompounds having analogous structures to the present compounds accordingto the invention.

Among the nitro-substituted heterocyclic compounds according to theinvention, of the formula (I), preferred compounds are those in which

R is hydrogen or C₁ -C₄ alkyl,

Z is C₆ -C₁₀ aryl, or a 5 to 6-membered heterocyclic group containing 1to 2 hetero atoms selected from the group consisting of O, S and N, atleast one of which is a nitrogen atom, and said aryl and heterocyclicgroup may be substituted respectively by any one member optionallyselected from the group consisting of halogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ haloalkyl, C₁ -C₄ alkylthio, C₁ -C₄ haloalkoxy, C₁ -C₄haloalkylthio, nitro, and cyano, A is ethylene or trimethylene, both ofwhich may be substituted by methyl, and

B stands for 2 or 3 members of a heterocyclic ring which is formed,together with the adjacent C-atom and N-atom, and at least one of saidmembers may represent a nitrogen atom or a sulfur atom and may beoptionally substituted by at least one selected from the groupconsisting of halogen, C₁ -C₆ alkyl, C₁ -C₄ alkoxy, alkoxycarbonylhaving 1 to 4 carbon atoms in the alkoxy part, optionally substituted C₆-C₁₀ aryl, keto, imino, phenoxy, C₁ -C₄ -alkylthio, alkoxycarbonyliminohaving 1 to 4 carbon atoms in the alkoxy part, phenoxycarbonylimino,benzoylimino, benzyl, cyano, thioketo, benzyl, hydroxy and C₁ -C₂alkylidene, provided that where B stands for 3 members, two of which arecarbon atoms and the other of which is a nitrogen atom which is locatedin the middle of the three members, then at least one of said two carbonatoms is substituted by a keto group.

Very particularly preferred nitro-substituted heterocyclic compounds ofthe formula (I) are those in which

R is hydrogen, or methyl,

Z is phenyl, or a 5 to 6-membered heterocylic group containing 1 to 2hetero atoms selected from the group consisting of O, S and N, at leastone of which is a nitrogen atom, and said phenyl and heterocyclic groupmay be optionally substituted by one or two selected optionally from thegroup consisting of fluorine, chlorine, bromine, methyl, ethyl, methoxy,trifluoromethyl, methylthio, trifluoromethoxy, trifluoromethylthio,nitro and cyano,

A is ethylene or trimethylene, both of which may be substituted bymethyl, and

B stands for 2 or 3 members of a heterocyclic ring which is formed,together with the adjacent C-atom and N-atom and at least one of saidmembers may represent a nitrogen atom or a sulfur atom and may beoptionally substituted by at least one substituent selected from thegroup consisting of fluorine, chlorine, bromine, methyl, methoxy,alkoxycarbonyl having 1 to 2 carbon atoms in the alkoxy part, phenyl,keto, imino, phenoxy, alkoxycarbonyl-imino having 1 to 2 carbon atoms inthe alkoxy part, phenoxycarbonyl-imino, benzoyl imino, benzyl, cyano,thicketo, benzyl, hydroxy, and C₁ -C₂ alkylidene, provided that where Bstands for 3 members, two of which are carbon atoms and the other one isa nitrogen atom which is located in the middle of the three members,then at least one of said two carbon atoms must be substituted by a ketogroup.

As individual examples of the compounds of the formula (I) according tothe invention, the following compounds can be mentioned: ##STR16##

In the above-mentioned process a), if use is made, as startingcompounds, for example, of 2-chloro-5-chloromethylpyridine, andethyl-1,2,3,5-tetrahydro-8-nitro-imidazo[1,2-a]pyridin-5-one-6-carboxylate,the reaction proceeds as follows: ##STR17##

In the above-mentioned process b), if use is made, as startingcompounds, for example, of 2-nitromethylene-3-(2-chloro-5-pyridylmethyl)imidazoline and propiolic acid methyl ester, the reaction proceeds asfollows: ##STR18##

In the compounds of the formula (II) in the abovementioned process a),R, Z and M have the same meanings as defined above.

In the formula (II), R and Z preferably have the preferred meaningsrespectively as indicated above, M is chlorine or tosyloxy.

The compounds of the formula (II) are already known in the art from, forexample, Japanese Patent Laid-open No. 81382/1987, and as individualexamples may be mentioned 2-chloro-5-chloromethylpyridine, and2-chloro-5-chloromethylthiazole.

In the compounds of the formula (III) in the process a), A and B havethe same meanings as defined above.

In the formula (III), A and B preferably have respectively the preferredmeanings as indicated above.

The compounds of the formula (III) include known ones described, forexample, in "Journal of Chemical Society Perkin" I, 1979, p. 2361,"Journal of Heterocyclic Chemistry", Vol. 17, p. 1413, and "ChemischeBerichte", Vol. 119, p. 2208.

A part of the compounds of the formula (III) can be obtained by reactingthe compounds represented by the following formula (XVII) ##STR19##wherein A has the same meaning as defined above, with compounds havingthe above-mentioned formulae (V), (VI) (VII), (VIII), (IX), (X), (XI),(XII), (XIII), (XIV), (XV) or (XVI), according to process b).

The compounds of the above formula (XVII) are already known, forexample, from Japanese Patent Laid-open No. 218,386/1985 and asindividual examples thereof can be mentioned,2-nitromethylene-imidazoline, and 2-nitromethylene-tetrahydropyrimidine.

Moreover, each of the compounds of the formulae (V), (VI), (VII),(VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV) and (XIV) arewell-known in the field of the organic chemistry.

Further, the compound represented, for example, by the following formula(XVIII), which corresponds to the formula (III); ##STR20## wherein A isthe same as above, n is 2 or 3, can be obtained by decomposing, by anacid, the compounds represented by the following formula (XIX) ##STR21##wherein A and n are the same as above, and subsequently cyclizing theproduct.

And the compounds of the above formula (XIX) can be obtained by reactingthe compound represented by the formula (XX),

    H.sub.2 N--A--NH--(CH.sub.2).sub.n --CH(OCH.sub.3).sub.2   (XX)

wherein A and n are the same as above,

with 1-nitro-2,2-bis(methylthio)ethylene.

The compounds of the above formula (XX) can be obtained by reacting thecompounds represented by the following formula (XXI),

    H.sub.2 N--A--NH.sub.2                                     (XXI)

wherein A is the same as above,

with the compounds represented by the following formula (XXII),

    Hal--(CH.sub.2).sub.n --CH(OCH.sub.3).sub.2                (XXII)

wherein n is the same as above, Hal is a halogen atom.

Both compounds of the above formulae (XXI) and (XXII) are knowncompounds.

In the compounds of the formula (IV) in the process b), R, Z and A haverespectively the same meanings as defined above.

In the formula (IV), R, Z and A preferably have respectively thepreferred meanings as mentioned above.

The compounds of the formula (IV) are already known, for example, fromJapanese Patent Laid-open Nos. 218,386/1985 and 183,271/1986, and asconcrete examples of the compounds can be mentioned, for example,

1-(2-chloro-5-pyridylmethyl)-2-nitromethyleneimidazolidine,

1-(2-chloro-5-pyridylmethyl)-2-nitromethylenetetrahydropyrimidine,

1-(2-chloro-5-thiazolylmethyl)-2-nitromethyleneimidazolidine,

1-(2-fluoro-5-pyridylmethyl)-2-nitromethyleneimidazolidine, and

1-(2-methyl-5-pyridylmethyl)-2-nitromethyleneimidazolidine.

In carrying out the process a) mentioned above, use may be made, assuitable diluent, of an inert solvents.

Examples of the solvent or diluents are water; aliphatic, cycloaliphaticand aromatic, optionally chlorinated, hydrocarbons, such as hexane,cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene,methylene chloride, chloroform, carbon tetrachloride, ethylene chloride,trichloroethylene, chlorobenzene and the like; ethers such as diethylether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propyleneoxide, dioxane, tetrahydrofuran and the like; nitriles such asacetonitrile, propionitrile, acrylonitrile and the like; alcohols suchas methanol, ethanol, iso-propanol, butanol, ethylene glycol and thelike; acid amides such as dimethyl formamide, dimethyl acetamide and thelike; and sulfones and sulfoxides such as dimethyl sulfoxide, sulfolaneand the like; bases, for example, hydrides such as sodium hydride,potassium hydrides, alkali metal hydroxides, carbonates and tertiaryamines such as triethylamine.

In the above-mentioned process a), the reaction temperature can bevaried within a wide range. In general, the reaction is carried out at atemperature of about 0° to 100° C., preferably about 10°-80° C.

In general, the reaction is allowed to proceed under normal pressure,although it is also possible to employ a higher or lower pressure.

When the above-mentioned process a) according to the invention iscarried out, use is made, for instance, of about 1.1 to 1.2 moles ofsodium hydride as a base, and about 1 to 1.2 moles, preferably about 1to 1.1 moles of the compounds of the formula (II) per 1 mole of thecompounds of the formula (III). The reaction may be conducted in thepresence of an inert solvent such as dimethyl sulfoxide, for example, toobtain the aimed compound.

When the above-mentioned process b) is carried out, it is possible toemploy whatever inert solvent similar to that used in the process a)according to the invention.

The above-mentioned process b) can be carried out at reactiontemperature varying within a wide range, for example, between about 0°C. and a boiling point of a mixture, preferably between about 0° C. andabout 100° C.

The reaction is preferably carried out under normal pressure, althoughit is also possible to employ a higher or lower pressure.

In the process b), the reaction of the compounds of the formula (IV)either with the compounds of the formula (VI) or with the compounds ofthe formula (VII) can be conducted in the similar manner to thereactions described in U.S. Pat. No. 4,033,954 and U.S. Pat. No.4,033,955.

Further, the reaction of the compounds of the formula (IV) either withthe compounds of the formula (IX) or with the compounds of the formula(X) can be conducted according to the reaction similar to that describedin "Journal fur Praktische Chemie", Vol. 319, p. 149.

The reaction of the compounds of the formula (IV) with the compounds ofthe formula (XII), or with the compounds of the formula (XIII), or withthe compounds of the formula (XIV) can be carried out according to thecommonly known Michael reaction.

The reaction of the compound having the formula (IV) with the compoundhaving the formula (XV) is carried out in the presence of a base to givethe desired nitro-substituted heterocyclic compound having the formula(Ia).

In the case where the formula (I) of the present invention isrepresented by the following formula (Ib), ##STR22## wherein R, Z, A,and R¹ are the same as above, said compounds can be obtained, separatelyfrom the above-mentioned processes a) and b), by reacting the compoundsof the formula (IV) with the compounds represented by the followingformula (XXIII), ##STR23## wherein R¹ is the same as above, andsubsequently reacting the reaction product with bromine.

The above reaction can be carried out according to the processesdescribed in publications of "Tetrahedron", Vol. 33, p. 1057, the sameVol. 37, p. 1470, and "Indian Journal of Chemistry", 15B, p. 886.

Further, if the compounds of the above formula (Ib) are hydrolyzedgently, the following compounds of the formula (Ic) which correspond tothe formula (I) of the present invention can be obtained ##STR24##wherein R, Z and A are the same as above.

In the above-mentioned reaction wherein the compounds of the formula(IV) are reacted with the compounds of the formula (XXIII), andsubsequently with bromine, if the reaction product, instead of beingreacted with bromine, is heated in the presence of a catalytic amount ofa base, then the following compounds of the formula (Id) whichcorrespond to the formula (I) of the present invention can be obtained##STR25## wherein R, Z and A are the same as above.

If the compounds of the formula (I) of the present invention arerepresented by the following formula (Ie) ##STR26## wherein R, Z, A andR¹ are the same as above, and R¹ s are identical with or different fromeach other,

the compounds of the formula (Ie) can be obtained by reacting thecompounds of the following formula (XXIV) ##STR27## wherein R, Z and Aand R¹ are the same as above, with the compounds of the followingformula (XXV),

    R.sup.1 --NCO                                              (XXV)

wherein R¹ is the same as above,

and the above reaction may be carried out according to the processdescribed in U.S. Pat. No. 3,985,735.

Further, the compounds of the above formula (XXIV) are known onesdescribed in Japanese Patent Laid-open No. 81382/1987, and it can beobtained according to the process described in the same.

The active compounds are well tolerated by plants, have a favorablelevel of toxicity to warm-blooded animals, and can be used for combatingarthropod pests, especially insects which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene field. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The above-mentioned pests include:

from the class of the Isopoda, for example Oniscus Asellus,Armadillidium vulgare and Porcellio scaber;

from the class of the Diplopoda, for example Blaniulus guttulatus;

from the class of the Chilopoda, for example Geophilus carpoghagus andScutigera spec.;

from the class of the Symphyla, for example Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the Collembola, for example Onychiurus armatus;

from the order of the Orthoptera; for example Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gyrllotalpa spp., Locusta migrato ria migratorioides,Melanoplus differentialis and Schistocerca gregaria;

from the order of the Dermaptera, for example Forficula auricularia;

from the order of the Isoptera, for example Reticultiermes spp.;

from the order of the Anoplura, for example Phylloxera vastatrix,Pemphiqus spp., Pediculus Humanus corporis, Haematopinus spp. andLinognathus spp.;

from the order of the Mallophaga, for example Trichodectes spp. andDamalinea spp.;

from the order of the Thysanoptera, for example Hercinothrips femoralisand Thrips tabaci,

from the order of the Heteroptera, for example Eurygaster spp.,Dysdercus intermedius, Piesma guadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.;

from the order of the Homoptera, for example Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saiessetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotusheterae, Pseudococcus spp. and Psylla spp.;

from the order of the Lepidoptera, for example Pectinophora gossypiella,Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella,Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria,Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella,Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Eariasinsulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsapomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestiakuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana,Choristoneura fumiferana, Clysia ambiguella, Homona magnanima andTortrix viridana;

from the order of the Coleoptera, for example Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelidesobtectus, Hylotruples bajulus, Agelastica alni, Leptinotarsadecemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodeschrysocephala, Epilachan varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus spp., Sitophilus spp., Othiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Meligethes aeneus, Ptinus spp., Niptus holoeucus, Gibbiuimpsylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderusspp., Melolontha melolontha, Amphimallon solstitialis and Costelytrazealandica;

from the order of the Hymenoptera for example Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.;

from the order of the Diptera, for example Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyamia, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

Furthermore, in the field of veterinary medicine, the novel compounds ofthe present invention can effectively be employed for combating avariety of noxious animal-parasitic pests (internal- andexternal-parasitic pests), e.g. parasitic insects and nemotodes. Suchanimal-parasitic pests may be exemplified as follows:

From the class of Insects, e.g. Gastrophilus spp., Stomoxys spp.,Tricodectes spp., Rhodnius spp., Ctenocephalides canis and the like.

By the term "pesticides" herein is meant a substance which exhibits acombating action on pests including those illustrated above.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances, coatingcompositions for use on seed, and formulations used with burningequipment, such as fumigating cartridges, fumigating cans and fumigatingcoils, as well as ULV cold mist and warm mist formulations.

These formulations may be produced in a known manner, for example bymixing the active compounds with extenders, that is to say liquid orliquefied gaseous or solid diluents or carriers, optionally with the useof surface-active agents, that is to say emulsifying agents and/ordispersing agents and/or foam-forming agents. If water is used as anextender, organic solvents can, for example, also be used as auxiliarysolvents.

As liquid solvents diluents or carriers, there are suitable in the main,aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes,chlorinated aromatic or chlorinated aliphatic hydrocarbons, such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons, such as cyclohexane or paraffins, for example, mineral oilfractions, alcohols, such as butanol or glycol as well as their ethersand esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, or strongly polar solvents, such asdimethylformamide and dimethyl-sulphoxide, as well as water.

By liquefied gaseous diluents or carriers liquids are meant which wouldbe gaseous at normal temperature and under normal pressure, for example,aerosol propellants such as halogenated hydrocarbons as well as butane,propane, nitrogen and carbon dioxide.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solids carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, corn cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example, alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulation.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain from 0.1 to 95 per cent by weight ofactive compound, preferably from 0.5 to 90 per cent by weight.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, baits, sterilising agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas, substances produced by microorganisms.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agents are compounds which increase the action ofthe active compounds, without it being necessary for the synergisticagent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to100% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

The invention will be further illustrated by way of examples. However,it should be noted that the scope of the invention is not limited onlyto the scope of the examples.

EXAMPLES OF SYNTHESIS Example 1 ##STR28##

A mixed solution of 2-nitromethylene-3-(2-chloro-5-pyridylmethyl)imidazolidine (12.7 g), propiolic acid methyl ester (4.2 g) and methanol(100 ml) was refluxed under heating for about 20 hours. Subsequentlymethanol was distilled off under reduced pressure, and the residue wasrefined by a silica-gel column chromatography to give the desired1,2,3,5-tetrahydro-1-(2-chloro-5-pyridylmethyl)-8-nitroimidazo[1,2-a]pyridin-5-one (8 g).

Example 2 ##STR29##

Ethyl-1,2,3,5-tetrahydro-8-nitro-5-oxaimidazo[1,2-a]pyridine-6-carboxylate (12.7 g) was dissolved in dry dimethyl-sulfoxide(60 ml), 60% sodium hydride (2 g) was added in small portions to thesolution in a stream of nitrogen gas at room temperature, and thenstirred at room temperature for an hour to obtain the sodium salt. Next,2-chloro-5-chloromethylpyridine (8.1 g) was added thereto at roomtemperature, and the content was stirred at room temperature for a day.The whole content was carefully poured out into 100 ml of ice cold waterto deposit the desired compound as crystals, which were filtered off andwashed with ethanol to give the desiredethyl-1,2,3,5-tetrahydro-1-(2-chloro-5-pyridimethyl)-8-nitro-imidzo[1,2-a]-5-one-6-carboxylate(12 g).

mp. 259°-263° C.

Example 3 ##STR30##

2-nitromethylene-3-(2-chloro-5-thiazolylmethyl)-imidazolidine (13 g) wassuspended in dry acetonitrile (100 ml.). Ethoxycarbonylisothiocyanate(6.6 g) was added to the above mentioned suspension at room temperature,successively refluxed under heating for 10 minutes. The content wasbrought to room temperature, and subsequently stirred for an hour todeposit crystals, which were filtered off.

Next, the crystals were suspended in acetic acid (60 ml), while beingstirred at a temperature of 10° C., and bromine (8 g) was addeddropwise. When the dropping was completed, it was stirred further for anhour to complete the reaction. Acetic acid was distilled off underreduced pressure, water was added to the residue to dissolve it, sodiumbicarbonate was added in small portions to the solution to make italkaline, and it was subsequently extracted twice with dichloromethane.After the dichloromethane layer was dried with sodium sulfate, thesolvent was distilled off, and the residue was recrystallized withethanol to give the desiredethyl-2,4,5,6-tetrahydro-4-(2-chloro-5-thiazylmethyl-3-nitro-imidazol[1,2-b]isothiazole-2-ylidenecarbamate(12 g).

Mp. 176°-180° C.

Compounds which can be prepared according to the same process as shownin the above Examples 1-3, together with the compounds of the Examples1-3, are listed in the following Table 1.

                                      TABLE 1                                     __________________________________________________________________________     ##STR31##                                                                     No.Compound                                                                         Z         R                                                                                ##STR32##  (C side) B (N side)                            __________________________________________________________________________           ##STR33##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR34##                                      2                                                                                    ##STR35##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR36##   mp. 199- 203° C.            3                                                                                    ##STR37##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR38##   mp. 91- 95° C.              4                                                                                    ##STR39##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR40##   mp. 259- 263° C.            5                                                                                    ##STR41##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR42##   mp. 205- 210° C.            6                                                                                    ##STR43##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR44##   mp. 131- 135° C.                                                       (decompo- sition)                  7                                                                                    ##STR45##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR46##   mp. 256- 260° C.            8                                                                                    ##STR47##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR48##   mp. 148- 150° C.            9                                                                                    ##STR49##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH         mp. 139- 143°C.             10                                                                                   ##STR50##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR51##   mp. 233- 237° C.                                                       (decompo- sition)                  11                                                                                   ##STR52##                                                                              H  CH.sub.2 CH.sub.2                                                                        CH.sub.2 CH.sub.2                               12                                                                                   ##STR53##                                                                              H  CH.sub.2 CH.sub.2                                                                        CH.sub.2 CH.sub.2                               13                                                                                   ##STR54##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR55##                                      14                                                                                   ##STR56##                                                                              H  (CH.sub.2).sub.3                                                                         CHCH                                            15                                                                                   ##STR57##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH                                            16                                                                                   ##STR58##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH                                            17                                                                                   ##STR59##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH                                            18                                                                                   ##STR60##                                                                              H                                                                                 ##STR61## CHCH                                            19                                                                                   ##STR62##                                                                              H  (CH.sub.2).sub.3                                                                          ##STR63##                                      20                                                                                   ##STR64##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR65##                                      21                                                                                   ##STR66##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR67##                                      22                                                                                   ##STR68##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH                                            23                                                                                   ##STR69##                                                                              H  (CH.sub.2).sub.3                                                                         CHCH                                            24                                                                                   ##STR70##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH                                            25                                                                                   ##STR71##                                                                              CH.sub.3                                                                         CH.sub.2 CH.sub.2                                                                        CH.sub.2 CH.sub.2                               26                                                                                   ##STR72##                                                                              H  CH.sub.2 CH.sub.2                                                                        CH CH                                           27                                                                                   ##STR73##                                                                              H  (CH.sub.2).sub.3                                                                          ##STR74##                                      28                                                                                   ##STR75##                                                                              H  CH.sub.2 CH.sub.2                                                                        CClCH                                           29                                                                                   ##STR76##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR77##                                      30                                                                                   ##STR78##                                                                              H  (CH.sub.2).sub.3                                                                         CHCH                                            31                                                                                   ##STR79##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH                                            32                                                                                   ##STR80##                                                                              H  (CH.sub.2).sub.3                                                                         CHCH                                            33                                                                                   ##STR81##                                                                              H  (CH.sub.2).sub.2                                                                         CHCH                                            34                                                                                   ##STR82##                                                                              H  CH.sub.2 CH.sub.2                                                                        CH.sub.2 CH.sub.2                               35                                                                                   ##STR83##                                                                              H  CH.sub.2 CH.sub.2                                                                        CHCH                                            36                                                                                   ##STR84##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR85##                                      37                                                                                   ##STR86##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR87##                                      38                                                                                   ##STR88##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR89##                                      39                                                                                   ##STR90##                                                                              CH.sub.3                                                                         (CH.sub.2).sub.3                                                                          ##STR91##                                      40                                                                                   ##STR92##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR93##                                      41                                                                                   ##STR94##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR95##                                      42                                                                                   ##STR96##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR97##                                      43                                                                                   ##STR98##                                                                              H  CH.sub.2 CH.sub.2                                                                         ##STR99##                                      44                                                                                   ##STR100##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR101##                                     45                                                                                   ##STR102##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR103##                                     46                                                                                   ##STR104##                                                                             H                                                                                 ##STR105##                                                                               ##STR106##                                     47                                                                                   ##STR107##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR108##                                     48                                                                                   ##STR109##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR110##                                     49                                                                                   ##STR111##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR112##                                     50                                                                                   ##STR113##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR114##                                     51                                                                                   ##STR115##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR116##                                     52                                                                                   ##STR117##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR118##                                     53                                                                                   ##STR119##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR120##                                     54                                                                                   ##STR121##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR122##                                     55                                                                                   ##STR123##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR124##                                     56                                                                                   ##STR125##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR126##                                     57                                                                                   ##STR127##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR128##                                     58                                                                                   ##STR129##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR130##                                     59                                                                                   ##STR131##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR132##                                     60                                                                                   ##STR133##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR134##                                     61                                                                                   ##STR135##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR136##                                     62                                                                                   ##STR137##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR138##                                     63                                                                                   ##STR139##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR140##  mp. 176- 180° C.            64                                                                                   ##STR141##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR142##                                     65                                                                                   ##STR143##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR144##                                     66                                                                                   ##STR145##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR146##                                     67                                                                                   ##STR147##                                                                             H  CH.sub.2 CH.sub.2                                                                        CHN                                             68                                                                                   ##STR148##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR149##                                     69                                                                                   ##STR150##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR151##                                     70                                                                                   ##STR152##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR153##                                     71                                                                                   ##STR154##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR155##                                     72                                                                                   ##STR156##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR157##                                     73                                                                                   ##STR158##                                                                             H  CH.sub.2 CH.sub.2                                                                        NN                                              74                                                                                   ##STR159##                                                                             H  CH.sub.2 CH.sub.2                                                                        NN                                              75                                                                                   ##STR160##                                                                             H  CH.sub.2 CH.sub.2                                                                        NN                                              76                                                                                   ##STR161##                                                                             H  CH.sub.2 CH.sub.2                                                                        CH.sub.2 CH.sub.2 CH.sub.2                      77                                                                                   ##STR162##                                                                             H  CH.sub.2 CH.sub.2                                                                        CH.sub.2 CH.sub.2 CH.sub.2                      78                                                                                   ##STR163##                                                                             H  (CH.sub.2).sub.3                                                                         CH.sub.2 CH.sub.2 CH.sub.2                      79                                                                                   ##STR164##                                                                             H  CH.sub.2 CH.sub.2                                                                        CH.sub.2 CH.sub.2 CH.sub.2                      80                                                                                   ##STR165##                                                                             H  CH.sub.2 CH.sub.2                                                                        CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2             81                                                                                   ##STR166##                                                                             H  CH.sub.2 CH.sub.2                                                                        CHCHCH.sub.2                                    82                                                                                   ##STR167##                                                                             H  (CH.sub.2).sub.3                                                                         CHCHCH.sub.2                                    83                                                                                   ##STR168##                                                                             H  CH.sub.2 CH.sub.2                                                                        CHCHCH.sub.2                                    84                                                                                   ##STR169##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR170##                                     85                                                                                   ##STR171##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR172##                                     86                                                                                   ##STR173##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR174##                                     87                                                                                   ##STR175##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR176##                                     88                                                                                   ##STR177##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR178##                                     89                                                                                   ##STR179##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR180##                                     90                                                                                   ##STR181##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR182##                                     91                                                                                   ##STR183##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR184##                                     92                                                                                   ##STR185##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR186##                                     93                                                                                   ##STR187##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR188##                                     94                                                                                   ##STR189##                                                                             CH.sub.3                                                                         CH.sub.2 CH.sub.2                                                                         ##STR190##                                     95                                                                                   ##STR191##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR192##                                     96                                                                                   ##STR193##                                                                             H  CH.sub.2 CH.sub. 2                                                                        ##STR194##                                     97                                                                                   ##STR195##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR196##                                     98                                                                                   ##STR197##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR198##                                     99                                                                                   ##STR199##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR200##                                     100                                                                                  ##STR201##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR202##                                     101                                                                                  ##STR203##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR204##                                     102                                                                                  ##STR205##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR206##                                     103                                                                                  ##STR207##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR208##                                     104                                                                                  ##STR209##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR210##                                     105                                                                                  ##STR211##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR212##                                     106                                                                                  ##STR213##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR214##                                     107                                                                                  ##STR215##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR216##                                     108                                                                                  ##STR217##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR218##                                     109                                                                                  ##STR219##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR220##                                     110                                                                                  ##STR221##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR222##                                     111                                                                                  ##STR223##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR224##                                     112                                                                                  ##STR225##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR226##                                     113                                                                                  ##STR227##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR228##                                     114                                                                                  ##STR229##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR230##                                     115                                                                                  ##STR231##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR232##                                     116                                                                                  ##STR233##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR234##                                     117                                                                                  ##STR235##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR236##                                     118                                                                                  ##STR237##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR238##                                     119                                                                                  ##STR239##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR240##                                     120                                                                                  ##STR241##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR242##                                     121                                                                                  ##STR243##                                                                             H  CH.sub.2 CH.sub. 2                                                                        ##STR244##                                     122                                                                                  ##STR245##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR246##                                     123                                                                                  ##STR247##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR248##                                     124                                                                                  ##STR249##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR250##  mp. 196- 200 ° C.           125                                                                                  ##STR251##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR252##                                     126                                                                                  ##STR253##                                                                             H  CH.sub. 2 CH.sub.2                                                                        ##STR254##  mp. >300° C.                127                                                                                  ##STR255##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR256##                                     128                                                                                  ##STR257##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR258##                                     129                                                                                  ##STR259##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR260##                                     130                                                                                  ##STR261##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR262##                                     131                                                                                  ##STR263##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR264##                                     132                                                                                  ##STR265##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR266##                                     133                                                                                  ##STR267##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR268##                                     134                                                                                  ##STR269##                                                                             H  CH.sub.2 CH.sub.2                                                                        CH.sub.2OCH.sub.2                               135                                                                                  ##STR270##                                                                             H  CH.sub.2 CH.sub.2                                                                        CH.sub.2OCH.sub.2                               136                                                                                  ##STR271##                                                                             H  CH.sub.2 CH.sub.2                                                                        CH.sub.2SCH.sub.2                               137                                                                                  ##STR272##                                                                             H  CH.sub.2 CH.sub.2                                                                        CHCH                                            138                                                                                  ##STR273##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR274##                                     139                                                                                  ##STR275##                                                                             H  CH.sub.2 CH.sub.2                                                                        CHCH                                            140                                                                                  ##STR276##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR277##                                     141                                                                                  ##STR278##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR279##                                     142                                                                                  ##STR280##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR281##                                     143                                                                                  ##STR282##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR283##                                     144                                                                                  ##STR284##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR285##                                     145                                                                                  ##STR286##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR287##                                     146                                                                                  ##STR288##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR289##                                     147                                                                                  ##STR290##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR291##                                     148                                                                                  ##STR292##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR293##                                     149                                                                                  ##STR294##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR295##                                     150                                                                                  ##STR296##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR297##                                     151                                                                                  ##STR298##                                                                             H  (CH.sub.2).sub.3                                                                         NN                                              152                                                                                  ##STR299##                                                                             H  CH.sub.2 CH.sub.2                                                                        CHCH                                            153                                                                                  ##STR300##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR301##                                     154                                                                                  ##STR302##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR303##                                     155                                                                                  ##STR304##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR305##  mp. 219- 222° C.            156                                                                                  ##STR306##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR307##                                     157                                                                                  ##STR308##                                                                             H  (CH.sub.2).sub.3                                                                          ##STR309##                                     158                                                                                  ##STR310##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR311##                                     159                                                                                  ##STR312##                                                                             H  CH.sub.2 CH.sub.2                                                                         ##STR313##                                     __________________________________________________________________________

Biotest Examples Control Compounds ##STR314## Example 4 Biotest carriedout against Nephotettix cinciticeps exhibiting resistance tooranophosphorus series insecticides

Preparation of test formulation:

Solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoxyethylene-alkylphenyl-ether

To prepare a suitable formulation of an active compound, 1 part byweight of the active compound was mixed with the above amount of thesolvent containing the above amount of the emulsifier, and the mixturewas diluted with water to the predetermined concentration.

Test method

Use was made of a plurality of pots each having a diameter of 12 cm inwhich were planted rice plant seedlings each having a height of about 10cm.

Onto each potted rice-plant seedling was sprayed 10 ml of an aqueoussolution of the above prepared active compound having the predeterminedconcentration.

After the sprayed solution was dried up, each of the pots was coveredwith a screen having a diameter of 7 cm and a height of 14 cm, in which30 pieces of female adults of Nephotettix cincticeps exhibitingresistance to organophosphorus-series insecticides were released, theneach pot was placed in a constant temperature chamber. Two days after,the number of the killed insects was counted to obtain the mortalityrate of the insects.

The test results were determined on an average basis, they are shown inTable 2.

                  TABLE 2                                                         ______________________________________                                                   Concentration of Insect                                            Compound No.                                                                             active compound in ppm                                                                         mortality in %                                    ______________________________________                                        1          200              100                                               4          200              100                                               6          200              100                                               8          200              100                                               9          200              100                                               Comparison                                                                    compounds                                                                     C-1        1000              20                                               C-2        1000              12                                               ______________________________________                                    

Example 5 Biotest carried out against Myzus persicae exhibitingresistance to organophosphorus and carbamate-series insecticides Testmethod

Onto eggplant seedlings (black long eggplant) each having a height of 20cm and planted on an unglazed pot having a diameter of 15 cm per oneseedling, 200 pieces of grown Myzus persicae having resistance againstorganophosphorus and carbamate-series insecticides were inoculated. Oneday after the inoculation, an aqueous solution having a predeterminedconcentration of the active compound, which had been prepared accordingto the procedure similar to Example 4, was sprayed onto the seedlingswith a sufficient dosage.

The above-mentioned test was carried out for each of the below-indicatedactive compounds with the indicated concentration dosages. After thespraying of the insecticidal solution, the seedlings in the pot for eachtest were allowed to stand for 24 hours in a green house kept at atemperature of 28° C., and, thereafter, the mortality rate of theinsects was determined for each test. The same test was repeated twicefor the purpose of obtaining an accurate mortality rate determination,the result of which is shown in the following Table 3:

                  TABLE 3                                                         ______________________________________                                                    Concentration of  Insect                                          Compound No.                                                                              active compound, ppm                                                                            mortality, %                                    ______________________________________                                        1           200               100                                             4           200               100                                             6           200               100                                             8           200               100                                             9           200               100                                             Comparison                                                                    compounds                                                                     C-1         1000               0                                              C-2         1000               0                                              ______________________________________                                    

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A nitro-substituted heterocyclic compound of theformula (I) ##STR315## wherein R is hydrogen or C₁ -C₄ alkyl,Z is C₆-C₁₀ aryl, or a 5 to 6-membered heterocylic group containing 1 to 2hetero atoms selected from the group consisting of O, S and N, at leastone of which is a nitrogen atom, and said aryl and heterocyclic group isunsubstituted or substituted respectively by one or two members selectedfrom the group consisting of halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁-C₄ haloalkyl, C₁ -C₄ alkylthio, C₁ -C₄ haloalkoxy, C₁ -C₄haloalkylthio, nitro, and cyano, A is ethylene which may be substitutedby methyl, and B stands for 2 members of a heterocyclic ring which isformed, together with the adjacent C-atom and N-atom, and at least oneof said members represents a nitrogen atom or a sulfur atom and themembers of B are unsubstituted or substituted by at least onesubstituent selected from the group consisting of halogen, C₁ -C₆ alkyl,C₁ -C₄ alkoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxypart, unsubstituted or substituted C₆ -C₁₀ aryl, keto, imino, phenoxy,C₁ -C₄ -alkylthio, alkoxycarbonylimino having 1 to 4 carbon atoms in thealkoxy part, phenoxycarbonylimino, benzoylimino, benzyl, cyano,thioketo, hydroxy and C₁ -C₂ alkylidene.
 2. A nitro-substitutedheterocyclic compound according to claim 1, whereinR is hydrogen, ormethyl, Z is phenyl, or a 5 to 6-membered heterocyclic group containing1 to 2 hetero atoms selected from the group consisting of O, S and N, atleast one of which is a nitrogen atom, and said phenyl and heterocyclicgroup are unsubstituted or substituted by one or two substituentsselected from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, methoxy, trifluoromethyl, methylthio, trifluoromethoxy,trifluoromethylthio, nitro and cyano, A is ethylene be substituted bymethyl, and B stands for 2 members of a heterocyclic ring which isformed, together with the adjacent C-atom and N-atom, and at least oneof said members represents a nitrogen atom or a sulfur atom and themembers of B are unsubstituted or substituted by at least onesubstituent selected from the group consisting of fluorine, chlorine,bromine, methyl, methoxy, alkoxycarbonyl having 1 to 2 carbon atoms inthe alkoxy part, phenyl, keto, imino, phenoxy, alkoxycarbonyl-iminohaving 1 to 2 carbon atoms in the alkoxy part, phenoxycarbonyl-imino,benzoyl imino, benzyl, cyano, thioketo, hydroxy, and C₁ -C₂ alkylidene.3. A nitro-substituted heterocyclic compound according to claim 1 of theformula ##STR316##
 4. An insecticidal composition comprising aninsecticidally effective amount of at least one nitro-substitutedheterocyclic compound according to claim 1 in admixture with a diluent.5. A method for combating harmful insects comprising applying to saidinsects and/or their habitat an insecticidally effective amount of atleast one nitro-substituted heterocyclic compound according to claim 1.6. A method according to claim 5, wherein the nitro-substitutedheterocyclic compound is of the formula ##STR317##